Triazolyl derivatives

ABSTRACT

Triazolyl derivatives ##STR1## in which R 1  and R 2  are identical or different and represent optionally substituted alkyl, optionally substituted alkenyl, optionally substituted cycloalkyl, optionally substituted aralkyl, optionally substituted aralkenyl, optionally substituted aroxyalkyl, optionally substituted aryl or optionally substituted heteroaryl and 
     X represents the groups --SH, --SR 3 , --SO--R 3 , --SO 2  --R 3  or --SO 3  H, in which 
     R 3  represents alkyl which is optionally substituted by fluorine and/or chlorine, alkenyl which is optionally substituted by fluorine and/or chlorine, optionally substituted aralkyl or optionally substituted aryl, 
      and their acid addition salts and metal salt complexes, 
     a plurality of processes for the preparation of the new substances, and their use as microbicides in plant protection and materials protection.

This application is a 371 of PCT/EP95/04392 filed Nov. 8, 1995.

The present invention relates to new triazolyl derivatives, to aplurality of processes for their preparation, and to their use asmicrobicides.

It has already been disclosed that a large number of hydroxyethyl-azolylderivatives have fungicidal properties (cf. EP-A 0 015 756, EP-A 0 040345, EP-A 0 052 424, EP-A 0 061 835 and EP-A 0 297 345). However, theapplicability of these substances is not always satisfactory in somecases.

There have now been found new triazolyl derivatives of the formula##STR2## in which R¹ and R² are identical or different and representoptionally substituted alkyl, optionally substituted alkenyl, optionallysubstituted cycloalkyl, optionally substituted aralkyl, optionallysubstituted aralkenyl, optionally substituted aroxyalkyl, optionallysubstituted aryl or optionally substituted heteroaryl and

X represents the groups --SH, --SR³, --SO--R³, --SO₂ --R³ or --SO₃ H, inwhich

R³ represents alkyl which is optionally substituted by fluorine and/orchlorine, alkenyl which is optionally substituted by fluorine and/orchlorine, optionally substituted aralkyl or optionally substituted aryl,

and their acid addition salts and metal salt complexes.

Those substances according to the invention in which R¹ and R² aredifferent have an asymmetrically substituted carbon atom. They cantherefore be obtained in the form of optical isomers. The presentinvention relates to the individual isomers as well as their mixtures.

Furthermore, it has been found that triazolyl derivatives of the formula(I) and their acid addition salts and metal salt complexes are obtainedwhen

a) hydroxyethyl-triazoles of the formula ##STR3## in which R¹ and R²have the abovementioned meanings, either

α) are reacted in succession with strong bases and sulphur in thepresence of a diluent and the product is then hydrolysed with water, ifappropriate in the presence of an acid, or

β) are reacted with sulphur in the presence of a high-boiling diluentand then treated, if appropriate, with water and, if appropriate, withacid,

and if appropriate the compounds resulting according to variants (α) and(β), of the formula ##STR4## in which R¹ and R² have the abovementionedmeanings, are reacted with halogen compounds of the formula

    R.sup.4 --Hal                                              (III)

in which

R⁴ represents alkyl which is optionally substituted by fluorine and/orchlorine, alkenyl which is optionally substituted by fluorine and/orchlorine or optionally substituted aralkyl and

Hal represents chlorine, bromine or iodine,

in the presence of an acid-binding agent and in the presence of adiluent and, if appropriate, the resulting compounds of the formula##STR5## in which R¹, R² and R⁴ have the abovementioned meanings, arereacted with oxidants in the presence of a diluent, or

b) hydroxyethyl-triazoles of the formula ##STR6## in which R¹ and R²have the abovementioned meanings, are reacted in succession with strongbases and diaryl disulphides of the formula

    R.sup.5 --S--S--R.sup.5                                    (IV)

in which

R⁵ represents optionally substituted aryl,

in the presence of a diluent and, if appropriate, the resultingcompounds of the formula ##STR7## in which R¹, R² and R⁵ have theabovementioned meanings, are reacted with oxidants in the presence of adiluent, or

c) triazolyl derivatives of the formula ##STR8## in which R¹ and R² havethe abovementioned meanings, are reacted with potassium permanganate inthe presence of a diluent,

and, if appropriate, the resulting compounds of the formula (I) are thensubjected to an addition reaction with an acid or a metal salt.

Finally, it has been found that the new triazolyl derivatives of theformula (I) and their acid addition salts and metal salt complexes havevery good microbicidal properties and can be used both in plantprotection and in materials protection to control undesirablemicroorganisms, such as fungi.

Surprisingly, the substances according to the invention have a bettermicrobicidal activity, in particular fungicidal activity than thosecompounds of the same direction of action which are most similarconstitutionally.

Formula (I) provides a general definition of triazolyl derivativesaccording to the invention.

R¹ preferably represents straight-chain or branched alkyl having 1 to 6carbon atoms, it being possible for these radicals to be monosubstitutedto tetrasubstituted by identical or different substituents from theseries consisting of halogen, alkoxy having 1 to 4 carbon atoms,alkoximino having 1 to 4 carbon atoms in the alkoxy moiety and/orcycloalkyl having 3 to 7 carbon atoms, or

represents straight-chain or branched alkenyl having 2 to 6 carbonatoms, it being possible for each of these radicals to bemonosubstituted to trisubstituted by identical or different substituentsfrom the series consisting of halogen, alkoxy having 1 to 4 carbon atomsand/or cycloalkyl having 3 to 7 carbon atoms, or

represents cycloalkyl having 3 to 7 carbon atoms, it being possible foreach of these radicals to be monosubstituted to trisubstituted byidentical or different substituents from the series consisting ofhalogen, cyano and/or alkyl having 1 to 4 carbon atoms, or

represents aralkyl having 6 to 10 carbon atoms in the aryl moiety and 1to 4 carbon atoms in the straight-chain or branched alkyl moiety, itbeing possible for the aryl moiety in each case to be monosubstituted totrisubstituted by identical or different substituents from the seriesconsisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkylhaving 1 or 2 carbon atoms and 1 to 5 identical or different halogenatoms, halogeno-alkoxy having 1 or 2 carbon atoms and 1 to 5 identicalor different halogen atoms, halogenoalkylthio having 1 or 2 carbon atomsand 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to7 carbon atoms, phenyl, phenoxy, alkoxycarbonyl having 1 to 4 carbonatoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbon atomsin the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, nitroand/or cyano, or

represents aralkenyl having 6 to 10 carbon atoms in the aryl moiety and2 to 4 carbon atoms in the alkenyl moiety, it being possible for thearyl moiety in each case to be monosubstituted to trisubstituted byidentical or different substituents from the series consisting ofhalogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbonatoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 or 2carbon atoms and 1 to 5 identical or different halogen atoms,halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 identical ordifferent halogen atoms, halogenoalkylthio having 1 or 2 carbon atomsand 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to7 carbon atoms, phenyl, phenoxy, alkoxycarbonyl having 1 to 4 carbonatoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbon atomsin the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, nitroand/or cyano, or

represents aroxyalkyl having 6 to 10 carbon atoms in the aryl moiety and1 to 4 carbon atoms in the straight-chain or branched oxyalkyl moiety,it being possible for the aryl moiety in each case to be monosubstitutedto trisubstituted by identical or different substituents from the seriesconsisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkylhaving 1 or 2 carbon atoms and 1 to 5 identical or different halogenatoms, halogeno-alkoxy having 1 or 2 carbon atoms and 1 to 5 identicalor different halogen atoms, halogenoalkylthio having 1 or 2 carbon atomsand 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to7 carbon atoms, phenyl, phenoxy, alkoxycarbonyl having 1 to 4 carbonatoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbon atomsin the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, nitroand/or cyano, or

represents aryl having 6 to 10 carbon atoms, it being possible for eachof these radicals to be monosubstituted to trisubstituted by identicalor different substituents from the series consisting of halogen, alkylhaving 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthiohaving 1 to 4 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 or2 carbon atoms and 1 to 5 identical or different halogen atoms,halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 identical ordifferent halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl,phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety,alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to4 carbon atoms in the alkyl moiety, nitro and/or cyano, or

represents an optionally benzo-fused five- or six-memberedheteroaromatic radical having 1 to 3 heteroatoms, such as nitrogen,sulphur and/or oxygen, it being possible for each of these radicals tobe monosubstituted to trisubstituted by identical or differentsubstituents from the series consisting of halogen, alkyl having 1 to 4carbon atoms, hydroxyalkyl having 1 to 4 carbon atoms, hydroxyalkinylhaving 3 to 8 carbon atoms, alkoxy having 1 or 2 carbon atoms, alkylthiohaving 1 or 2 carbon atoms, halogenoalkyl, halogenoalkoxy andhalogenoalkylthio, each of which has 1 or 2 carbon atoms and 1 to 5identical or different halogen atoms, such as fluorine or chlorineatoms, formyl, dialkoxymethyl having 1 or 2 carbon atoms in each alkoxygroup, acyl having 2 to 4 carbon atoms, alkoxycarbonyl having 1 to 4carbon atoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbonatoms in the alkoxy moiety and 1 to 3 carbon atoms in the alkyl moiety,nitro and/or cyano.

R² preferably represents straight-chain or branched alkyl having 1 to 6carbon atoms, it being possible for these radicals to be monosubstitutedto tetra-substituted by identical or different substituents from theseries consisting of halogen, alkoxy having 1 to 4 carbon atoms,alkoximino having 1 to 4 carbon atoms in the alkoxy moiety and/orcycloalkyl having 3 to 7 carbon atoms, or

represents straight-chain or branched alkenyl having 2 to 6 carbonatoms, it being possible for each of these radicals to bemonosubstituted to trisubstituted by identical or different substituentsfrom the series consisting of halogen, alkoxy having 1 to 4 carbon atomsand/or cycloalkyl having 3 to 7 carbon atoms, or

represents cycloalkyl having 3 to 7 carbon atoms, it being possible foreach of these radicals to be monosubstituted to trisubstituted byidentical or different substituents from the series consisting ofhalogen, cyano and/or alkyl having 1 to 4 carbon atoms, or

represents aralkyl having 6 to 10 carbon atoms in the aryl moiety and 1to 4 carbon atoms in the straight-chain or branched alkyl moiety, itbeing possible for the aryl moiety in each case to be monosubstituted totrisubstituted by identical or different substituents from the seriesconsisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkylhaving 1 or 2 carbon atoms and 1 to 5 identical or different halogenatoms, halogeno-alkoxy having 1 or 2 carbon atoms and 1 to 5 identicalor different halogen atoms, halogenoalkylthio having 1 or 2 carbon atomsand 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to7 carbon atoms, phenyl, phenoxy, alkoxycarbonyl having 1 to 4 carbonatoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbon atomsin the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, nitroand/or cyano, or

represents aralkenyl having 6 to 10 carbon atoms in the aryl moiety and2 to 4 carbon atoms in the alkenyl moiety, it being possible for thearyl moiety in each case to be monosubstituted to trisubstituted byidentical or different substituents from the series consisting ofhalogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbonatoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 or 2carbon atoms and 1 to 5 identical or different halogen atoms,halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 identical ordifferent halogen atoms, halogenoalkylthio having 1 or 2 carbon atomsand 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to7 carbon atoms, phenyl, phenoxy, alkoxycarbonyl having 1 to 4 carbonatoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbon atomsin the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, nitroand/or cyano, or

represents aroxyalkyl having 6 to 10 carbon atoms in the aryl moiety and1 to 4 carbon atoms in the straight-chain or branched oxyalkyl moiety,it being possible for the aryl moiety in each case to be monosubstitutedto trisubstituted by identical or different substituents from the seriesconsisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkylhaving 1 or 2 carbon atoms and 1 to 5 identical or different halogenatoms, halogeno-alkoxy having 1 or 2 carbon atoms and 1 to 5 identicalor different halogen atoms, halogenoalkylthio having 1 or 2 carbon atomsand 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to7 carbon atoms, phenyl, phenoxy, alkoxycarbonyl having 1 to 4 carbonatoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbon atomsin the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, nitroand/or cyano, or

represents aryl having 6 to 10 carbon atoms, it being possible for eachof these radicals to be monosubstituted to trisubstituted by identicalor different substituents from the series consisting of halogen, alkylhaving 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthiohaving 1 to 4 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 or2 carbon atoms and 1 to 5 identical or different halogen atoms,halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 identical ordifferent halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl,phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety,alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to4 carbon atoms in the alkyl moiety, nitro and/or cyano, or

represents an optionally benzo-fused five- or six-memberedheteroaromatic radical having 1 to 3 heteroatoms, such as nitrogen,sulphur and/or oxygen, it being possible for each of these radicals tobe monosubstituted to trisubstituted by identical or differentsubstituents from the series consisting of halogen, alkyl having 1 to 4carbon atoms, hydroxyalkyl having 1 to 4 carbon atoms, hydroxyalkinylhaving 3 to 8 carbon atoms, alkoxy having 1 or 2 carbon atoms, alkylthiohaving 1 or 2 carbon atoms, halogenoalkyl, halogenoalkoxy andhalogenoalkylthio, each of which has 1 or 2 carbon atoms and 1 to 5identical or different halogen atoms, such as fluorine or chlorineatoms, formyl, dialkoxymethyl having 1 or 2 carbon atoms in each alkoxygroup, acyl having 2 to 4 carbon atoms, alkoxycarbonyl having 1 to 4carbon atoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbonatoms in the alkoxy moiety and 1 to 3 carbon atoms in the alkyl moiety,nitro and/or cyano.

X also preferably represents the groups --SH, --SR³, --SO--R³, --SO₂--R³ or --SO₃ H.

R³ preferably represents straight-chain or branched alkyl having 1 to 6carbon atoms, it being possible for each of these radicals to bemonosubstituted to trisubstituted by fluorine and/or chlorine, or

represents straight-chain or branched alkenyl having 2 to 6 carbonatoms, it being possible for each of these radicals to bemonosubstituted to trisubstituted by fluorine and/or chlorine, or

represents phenylalkyl having 1 to 4 carbon atoms in the straight-chainor branched alkyl moiety, it being possible for each of these radicalsto be monosubstituted to trisubstituted in the phenyl moiety byidentical or different substituents from the series consisting ofhalogen, alkyl having 1 to 4 carbon atoms, and/or halogenoalkyl having 1to 4 carbon atoms and 1 to 5 halogen atoms, or

represents phenyl which can be monosubstituted to trisubstituted byidentical or different substituents from the series consisting ofhalogen, alkyl having 1 to 4 carbon atoms, and/or halogenoalkyl having 1to 4 carbon atoms and 1 to 5 halogen atoms.

R¹ particularly preferably represents straight-chain or branched alkylhaving 1 to 4 carbon atoms, it being possible for these radicals to bemonosubstituted to tetrasubstituted by identical or differentsubstituents from the series consisting of fluorine, chlorine, bromine,methoxy, ethoxy, propoxy, isopropoxy, alkoximino having 1 or 2 carbonatoms in the alkoxy moiety, cyclopropyl, cyclobutyl, cyclopentyl and/orcyclohexyl, or

represents straight-chain or branched alkenyl having 2 to 5 carbonatoms, it being possible for each of these radicals to bemonosubstituted to trisubstituted by identical or different substituentsfrom the series consisting of fluorine, chlorine, bromine, methoxy,ethoxy, propoxy, isopropoxy, cyclopropyl, cyclobutyl, cyclopentyl and/orcyclohexyl, or

represents cycloalkyl having 3 to 6 carbon atoms, it being possible foreach of these radicals to be monosubstituted to trisubstituted byidentical or different substituents from the series consisting offluorine, chlorine, bromine, cyano, methyl, ethyl, propyl, ispropyland/or tert-butyl, or

represents phenylalkyl having 1 to 4 carbon atoms in the straight-chainor branched alkyl moiety, it being possible for the phenyl moiety to bemonosubstituted to trisubstituted by identical or different substituentsfrom the series consisting of fluorine, chlorine, bromine, methyl,ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl,trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy,difluoromethoxy, chlorodifluoromethylthio, methoxycarbonyl,ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl, nitro and/orcyano, or

represents phenylalkenyl having 2 to 4 carbon atoms in the alkenylmoiety, it being possible for the phenyl moiety to be monosubstituted totrisubstituted by identical or different substituents from the seriesconsisting of fluorine, chlorine, bromine, methyl, ethyl, tert-butyl,methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy,trifluoromethylthio, chlorodifluoromethoxy, difluoromethoxy,chlorodifluoromethylthio, methoxycarbonyl, ethoxycarbonyl,methoximino-methyl, 1-methoximinoethyl, nitro and/or cyano, or

represents phenoxyalkyl having 1 to 4 carbon atoms in the straight-chainor branched oxyalkyl moiety, it being possible for the phenyl moiety tobe monosubstituted to trisubstituted by identical or differentsubstituents from the series consisting of fluorine, chlorine, bromine,methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl,trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy,difluoromethoxy, chlorodifluoromethylthio, methoxycarbonyl,ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl, nitro and/orcyano, or

represents phenyl which can be monosubstituted to trisubstituted byidentical or different substituents from the series consisting offluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy,methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,chlorodifluoromethoxy, difluoromethoxy, chlorodifluoromethylthio,methoxycarbonyl, ethoxycarbonyl, methoximino-methyl, 1-methoximinoethyl,nitro and/or cyano, or

represents pyrazolyl, imidazolyl, 1,2,4-triazolyl, pyrrolyl, furanyl,thienyl, thiazolyl, oxazolyl, pyridinyl, pyrimidinyl, triazinyl,quinolinyl, isoquinolinyl, quinazolinyl, indolyl, benzothienyl,benzofuranyl, benzothiazolyl or benzimidazolyl, it being possible foreach of these radicals to be monosubstituted to trisubstituted byidentical or different substituents from the series consisting offluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy,methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,chlorodifluoromethoxy, chlorodifluoromethylthio, hydroxymethyl,hydroxyethyl, hydroxyalkinyl having 4 to 6 carbon atoms,methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl,nitro and/or cyano, formyl, dimethoxymethyl, acetyl and/or propionyl.

R² particularly preferably represents straight-chain or branched alkylhaving 1 to 4 carbon atoms, it being possible for these radicals to bemonosubstituted to tetrasubstituted by identical or differentsubstituents from the series consisting of fluorine, chlorine, bromine,methoxy, ethoxy, propoxy, isopropoxy, alkoximino having 1 or 2 carbonatoms in the alkoxy moiety, cyclopropyl, cyclobutyl, cyclopentyl and/orcyclohexyl, or

represents straight-chain or branched alkenyl having 2 to 5 carbonatoms, it being possible for each of these radicals to bemonosubstituted to trisubstituted by identical or different substituentsfrom the series consisting of fluorine, chlorine, bromine, methoxy,ethoxy, propoxy, isopropoxy, cyclopropyl, cyclobutyl, cyclopentyl and/orcyclohexyl, or

represents cycloalkyl having 3 to 6 carbon atoms, it being possible foreach of these radicals to be monosubstituted to trisubstituted byidentical or different substituents from the series consisting offluorine, chlorine, bromine, cyano, methyl, ethyl, propyl, isopropyland/or tert-butyl, or

represents phenylalkyl having 1 to 4 carbon atoms in the straight-chainor branched alkyl moiety, it being possible for the phenyl moiety to bemonosubstituted to trisubstituted by identical or different substituentsfrom the series consisting of fluorine, chlorine, bromine, methyl,ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl,trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy,difluoromethoxy, chloro-difluoromethylthio, methoxycarbonyl,ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl, nitro and/orcyano, or

represents phenylalkenyl having 2 to 4 carbon atoms in the alkenylmoiety, it being possible for the phenyl moiety to be monosubstituted totrisubstituted by identical or different substituents from the seriesconsisting of fluorine, chlorine, bromine, methyl, ethyl, tert-butyl,methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy,trifluoromethylthio, chlorodifluoromethoxy, difluoromethoxy,chlorodifluoromethylthio, methoxycarbonyl, ethoxycarbonyl,methoximinomethyl, 1-methoximinoethyl, nitro and/or cyano, or

represents phenoxyalkyl having 1 to 4 carbon atoms in the straight-chainor branched oxyalkyl moiety, it being possible for the phenyl moiety tobe monosubstituted to trisubstituted by identical or differentsubstituents from the series consisting of fluorine, chlorine, bromine,methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl,trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy,difluoromethoxy, chlorodifluoromethylthio, methoxycarbonyl,ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl, nitro and/orcyano, or

represents phenyl which can be monosubstituted to trisubstituted byidentical or different substituents from the series consisting offluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy,methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,chlorodifluoromethoxy, difluoromethoxy, chlorodifluoromethylthio,methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl,nitro and/or cyano, or

represents pyrazolyl, imidazolyl, 1,2,4-triazolyl, pyrrolyl, furanyl,thienyl, thiazolyl, oxazolyl, pyridinyl, pyrimidinyl, triazinyl,quinolinyl, isoquinolinyl, quinazolinyl, indolyl, benzothienyl,benzofuranyl, benzothiazolyl or benzimidazolyl, it being possible foreach of these radicals to be monosubstituted to trisubstituted byidentical or different substituents from the series consisting offluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy,methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,chlorodifluoromethoxy, chlorodifluoromethylthio, hydroxymethyl,hydroxyethyl, hydroxyalkinyl having 4 to 6 carbon atoms,methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl,nitro and/or cyano, formyl, dimethoxymethyl, acetyl and/or propionyl.

X also particularly preferably represents the groups --SH, --SR³,--SO--R³, --SO₂ --R³ or --SO₃ H.

R³ particularly preferably represents straight-chain or branched alkylhaving 1 to 4 carbon atoms, it being possible for each of these radicalsto be monosubstituted to trisubstituted by fluorine and/or chlorine, or

represents straight-chain or branched alkenyl having 2 to 5 carbonatoms, it being possible for each of these radicals to bemonosubstituted to trisubstituted by identical or different substituentsfrom the series consisting of fluorine and/or chlorine, or

represents phenylalkyl having 1 to 3 carbon atoms in the straight-chainor branched alkyl moiety, it being possible for each of these radicalsto be monosubstituted to trisubstituted in the phenyl moiety byidentical or different substituents from the series consisting offluorine, chlorine, bromine, methyl, ethyl, tert-butyl, trichloromethyland/or trifluoromethyl, or

represents phenyl which can be monosubstituted to trisubstituted byidentical or different substituents from the series consisting offluorine, chlorine, bromine, methyl, ethyl, tert-butyl, trichloromethyl.

R¹ very particularly preferably represents n-propyl, isopropyl, n-butyl,i-butyl, sec-butyl or tert-butyl, it being possible for these radicalsto be monosubstituted to tetrasubstituted by identical or differentsubstituents from the series consisting of fluorine, chlorine, bromine,methoxy, ethoxy, propoxy, isopropoxy, methoximino, ethoximino,cyclopropyl, cyclobutyl, cyclopentyl and/or cyclohexyl, or

represents straight-chain or branched alkenyl having 2 to 5 carbonatoms, it being possible for each of these radicals to bemonosubstituted to trisubstituted by identical or different substituentsfrom the series consisting of fluorine, chlorine, bromine, methoxy,ethoxy, propoxy, isopropoxy, cyclopropyl, cyclobutyl, cyclopentyl and/orcyclohexyl, or

represents 1-methyl-cyclohexyl, cyclohexyl, 1-chloro-cyclopropyl,1-fluorocyclopropyl, 1-methyl-cyclopropyl, 1-cyano-cyclopropyl,cyclopropyl, 1-methyl-cyclopentyl or 1-ethyl-cyclopentyl, or

represents phenylalkyl having 1 or 2 carbon atoms in the straight-chainor branched alkyl moiety, it being possible for the phenyl moiety to bemonosubstituted to trisubstituted by identical or different substituentsfrom the series consisting of fluorine, chlorine, bromine, methyl,ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl,trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy,difluoromethoxy, chlorodifluoromethylthio, methoxycarbonyl,ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl, nitro and/orcyano, or

represents phenylalkenyl having 2 to 4 carbon atoms in the alkenylmoiety, it being possible for the phenyl moiety to be monosubstituted totrisubstituted by identical or different substituents from the seriesconsisting of fluorine, chlorine, bromine, methyl, ethyl, tert-butyl,methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy,trifluoromethylthio, chlorodifluoromethoxy, difluoromethoxy,chlorodifluoromethylthio, methoxycarbonyl, ethoxycarbonyl,methoximinomethyl, 1-methoximinoethyl, nitro and/or cyano, or

represents phenoxyalkyl having 1 to 4 carbon atoms in the straight-chainor branched oxyalkyl moiety, it being possible for the phenyl moiety tobe monosubstituted to trisubstituted by identical or differentsubstituents from the series consisting of fluorine, chlorine, bromine,methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl,trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy,difluoromethoxy, chlorodifluoromethylthio, methoxycarbonyl,ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl, nitro and/orcyano, or

represents phenyl which can be monosubstituted to trisubstituted byidentical or different substituents from the series consisting offluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy,methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,chlorodifluoromethoxy, difluoromethoxy chlorodifluoromethylthio,methoxycarbonyl, ethoxycarbonyl, methoximino-methyl, 1-methoximinoethyl,nitro and/or cyano, or represents pyrazolyl, imidazolyl,1,2,4-triazolyl, pyrrolyl, furanyl, thienyl, thiazolyl, oxazolyl,pyridinyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl,quinazolinyl, indolyl, benzothienyl, benzofuranyl, benzothiazolyl orbenzimidazolyl, it being possible for each of these radicals to bemonosubstituted to trisubstituted by identical or different substituentsfrom the series consisting of fluorine, chlorine, bromine, methyl,ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl,trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy,chlorodifluoromethylthio, hydroxymethyl, hydroxyethyl, hydroxyalkinylhaving 4 to 6 carbon atoms, methoxycarbonyl, ethoxycarbonyl,methoximinomethyl, 1-methoximinoethyl, nitro and/or cyano, formyl,dimethoxymethyl, acetyl and/or propionyl.

R² very particularly preferably represents n-propyl, isopropyl, n-butyl,i-butyl, sec-butyl or tert-butyl, it being possible for these radicalsto be monosubstituted to tetrasubstituted by identical or differentsubstituents from the series consisting of fluorine, chlorine, bromine,methoxy, ethoxy, propoxy, isopropoxy, methoximino, ethoximino,cyclopropyl, cyclobutyl, cyclopentyl and/or cyclohexyl, or

represents straight-chain or branched alkenyl having 2 to 5 carbonatoms, it being possible for each of these radicals to bemonosubstituted to trisubstituted by identical or different substituentsfrom the series consisting of fluorine, chlorine, bromine, methoxy,ethoxy, propoxy, isopropoxy, cyclopropyl, cyclobutyl, cyclopentyl and/orcyclohexyl, or

represents 1-methyl-cyclohexyl, cyclohexyl, 1-chloro-cyclopropyl,1-fluorocyclopropyl, 1-methyl-cyclopropyl, 1-cyano-cyclopropyl,cyclopropyl, 1-methyl-cyclopentyl or 1-ethyl-cyclopentyl, or

represents phenylalkyl having 1 or 2 carbon atoms in the straight-chainor branched alkyl moiety, it being possible for the phenyl moiety to bemonosubstituted to trisubstituted by identical or different substituentsfrom the series consisting of fluorine, chlorine, bromine, methyl,ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl,trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy,difluoromethoxy, chlorodifluoromethylthio, methoxycarbonyl,ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl, nitro and/orcyano, or

represents phenylalkenyl having 2 to 4 carbon atoms in the alkenylmoiety, it being possible for the phenyl moiety to be monosubstituted totrisubstituted by identical or different substituents from the seriesconsisting of fluorine, chlorine, bromine, methyl, ethyl, tert-butyl,methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy,trifluoromethylthio, chlorodifluoromethoxy, difluoromethoxy,chlorodifluoromethylthio, methoxycarbonyl, ethoxycarbonyl,methoximino-methyl, 1-methoximinoethyl, nitro and/or cyano, or

represents phenoxyalkyl having 1 to 4 carbon atoms in the straight-chainor branched oxyalkyl moiety, it being possible for the phenyl moiety tobe monosubstituted to trisubstituted by identical or differentsubstituents from the series consisting of fluorine, chlorine, bromine,methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl,trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy,difluoromethoxy, chlorodifluoromethylthio, methoxycarbonyl,ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl, nitro and/orcyano, or

represents phenyl which can be monosubstituted to trisubstituted byidentical or different substituents from the series consisting offluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy,methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,chlorodifluoromethoxy, difluoromethoxy, chlorodifluoromethylthio,methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl,nitro and/or cyano, or

represents pyrazolyl, imidazolyl, 1,2,4-triazolyl, pyrrolyl, furanyl,thienyl, thiazolyl, oxazolyl, pyridinyl, pyrimidinyl, triazinyl,quinolinyl, isoquinolinyl, quinazolinyl, indolyl, benzothienyl,benzofuranyl, benzothiazolyl or benzimidazolyl, it being possible foreach of these radicals to be monosubstituted to trisubstituted byidentical or different substituents from the series consisting offluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy,methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,chlorodifluoromethoxy, chlorodifluoromethylthio, hydroxymethyl,hydroxyethyl, hydroxyalkinyl having 4 to 6 carbon atoms,methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl,nitro and/or cyano, formyl, dimethoxymethyl, acetyl and/or propionyl.

X also very particularly preferably represents the groups --SH, --SR³,--SO--R³, --SO₂ --R³ or --SO₃ H.

R³ very particularly preferably represents methyl, ethyl or propyl, itbeing possible for each of these radicals to be monosubstituted totrisubstituted by identical or different substituents from the seriesconsisting of fluorine and/or chlorine, or

represents allyl, but-2-en-yl or but-3-enyl, it being possible for eachof these radicals to be monosubstituted to trisubstituted by identicalor different substituents from the series consisting of fluorine and/orchlorine, or

represents phenylalkyl having 1 or 2 carbon atoms in the straight-chainor branched alkyl moiety, it being possible for each of these radicalsto be monosubstituted or disubstituted in the phenyl moiety by fluorine,chlorine, bromine, methyl, ethyl, tert-butyl, trichloromethyl and/ortrifluoromethyl, or

represents phenyl which can be monosubstituted or disubstituted byfluorine, chlorine, bromine, methyl, ethyl, tert-butyl, trichloromethyland/or trifluoromethyl.

Other preferred compounds according to the invention are adducts ofacids and those triazolyl derivatives of formula (I), in which R¹, R²and X have those meanings which have been mentioned as being preferredfor these substituents.

The acids which can be subjected to an addition reaction preferablyinclude hydrohalic acids, such as, for example, hydrochloric acid andhydrobromic acid, in particular hydrochloric acid, furthermorephosphoric acid, nitric acid, mono- and bifunctional carboxylic acidsand hydroxycarboxylic acids, such as, for example, acetic acid, maleicacid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylicacid, sorbic acid and lactic acid, and also sulphonic acids, such as,for example, p-toluenesulphonic acid and 1,5-naphthalenedisulphonic acidas well as saccharin and thiosaccharin.

Other preferred compounds according to the invention are adducts ofsalts of metals of main groups II to IV and sub-groups I and II and IVto VIII of the Periodic Table of the Elements and those triazolylderivatives of the formula (I), in which R¹, R² and X have thosemeanings which have been mentioned as being preferred for thesesubstituents.

Salts of copper, zinc, manganese, magnesium, tin, iron and nickel areparticularly preferred in this context. Suitable anions of these saltsare those which are derived from acids which lead to physiologicallyacceptable adducts. Particularly preferred acids of this type are, inthis context, the hydrohalic acids, such as, for example, hydrochloricacid and hydrobromic acid, furthermore phosphoric acid, nitric acid andsulphuric acid.

The triazolyl derivatives of the formula (I) according to the invention,in which X represents an --SH group, can be present in the "mercapto"form of the formula ##STR9## or in the tautomeric "thiono" form of theformula ##STR10## For the sake of simplicity, only the "mercapto" formis shown in each case.

Examples of substances according to the invention which may be mentionedare the triazolyl derivatives listed in the table which follows.

                                      TABLE 1                                     __________________________________________________________________________     ##STR11##                                                                    R.sup.1         R.sup.2 X                                                     __________________________________________________________________________     ##STR12##      C(CH.sub.3).sub.3                                                                     SH                                                     ##STR13##      C(CH.sub.3).sub.3                                                                     SCH.sub.3                                              ##STR14##      C(CH.sub.3).sub.3                                                                     SOCH.sub.3                                             ##STR15##      C(CH.sub.3).sub.3                                                                     SO.sub.2 CH.sub.3                                      ##STR16##      C(CH.sub.3).sub.3                                                                      ##STR17##                                             ##STR18##      C(CH.sub.3).sub.3                                                                     SO.sub.3 H                                             ##STR19##      C(CH.sub.3).sub.3                                                                     SCH.sub.2 CHCH.sub.2                                   ##STR20##      C(CH.sub.3).sub.3                                                                     SH                                                     ##STR21##      C(CH.sub.3).sub.3                                                                     SCH.sub.3                                              ##STR22##      C(CH.sub.3).sub.3                                                                     SOCH.sub.3                                             ##STR23##      C(CH.sub.3).sub.3                                                                     SO.sub.2 CH.sub.3                                      ##STR24##      C(CH.sub.3).sub.3                                                                      ##STR25##                                             ##STR26##      C(CH.sub.3).sub.3                                                                     SCH.sub.2 CHCH.sub.2                                   ##STR27##      C(CH.sub.3).sub.3                                                                     SH                                                     ##STR28##      C(CH.sub.3).sub.3                                                                     SCH.sub.3                                              ##STR29##      C(CH.sub.3).sub.3                                                                      ##STR30##                                             ##STR31##      C(CH.sub.3).sub.3                                                                     SCH.sub.2 CHCH.sub.2                                   ##STR32##                                                                                     ##STR33##                                                                            SH                                                     ##STR34##                                                                                     ##STR35##                                                                            SCH.sub.3                                              ##STR36##                                                                                     ##STR37##                                                                             ##STR38##                                             ##STR39##                                                                                     ##STR40##                                                                            SCH.sub.2 CHCH.sub.2                                   ##STR41##      C.sub.4 H.sub.9 -n                                                                    SH                                                     ##STR42##      C.sub.4 H.sub.9 -n                                                                    SCH.sub.3                                              ##STR43##      C.sub.4 H.sub.9 -n                                                                     ##STR44##                                             ##STR45##      C.sub.4 H.sub.9 -n                                                                    SCH.sub.2 CHCH.sub.2                                   ##STR46##                                                                                     ##STR47##                                                                            SH                                                     ##STR48##                                                                                     ##STR49##                                                                            SCH.sub.3                                              ##STR50##                                                                                     ##STR51##                                                                             ##STR52##                                             ##STR53##                                                                                     ##STR54##                                                                            SCH.sub.2 CHCH.sub.2                                   ##STR55##      C(CH.sub.3).sub.3                                                                     SH                                                     ##STR56##      C(CH.sub.3).sub.3                                                                     SCH.sub.3                                              ##STR57##      C(CH.sub.3).sub.3                                                                      ##STR58##                                             ##STR59##      C(CH.sub.3).sub.3                                                                     SCH.sub.2 CHCH.sub.2                                  Cl.sub.2 CHCCl.sub.2 CH.sub.2                                                                 C(CH.sub.3).sub.3                                                                     SH                                                    Cl.sub.2 CHCCl.sub.2 CH.sub.2                                                                 C(CH.sub.3).sub.3                                                                     SCH.sub.3                                             Cl.sub.2 CHCCl.sub.2 CH.sub.2                                                                  ##STR60##                                                                            SH                                                    Cl.sub.2 CHCCl.sub.2 CH.sub.2                                                                  ##STR61##                                                                            SCH.sub.3                                             Cl.sub.2 CHCCl.sub.2 CH.sub.2                                                                  ##STR62##                                                                            SH                                                    Cl.sub.2 CHCCl.sub.2 CH.sub.2                                                                  ##STR63##                                                                            SCH.sub.3                                              ##STR64##      C(CH.sub.3).sub.3                                                                     SH                                                     ##STR65##      C(CH.sub.3).sub.3                                                                     SCH.sub.3                                              ##STR66##                                                                                     ##STR67##                                                                            SCH.sub.3                                              ##STR68##                                                                                     ##STR69##                                                                            SCH.sub.3                                              ##STR70##                                                                                     ##STR71##                                                                            SCH.sub.3                                              ##STR72##                                                                                     ##STR73##                                                                            SCH.sub.3                                              ##STR74##                                                                                     ##STR75##                                                                            SCH.sub.3                                             Cl.sub.2 CHCCl.sub.2                                                                           ##STR76##                                                                            SCH.sub.3                                              ##STR77##      C(CH.sub.3).sub.3                                                                     SCH.sub.3                                              ##STR78##      C(CH.sub.3).sub.3                                                                     SCH.sub.3                                              ##STR79##      C(CH.sub.3).sub.3                                                                      ##STR80##                                            __________________________________________________________________________

If2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-olis used as starting substance, n-butyl-lithium as strong base andsulphur powder as reactant, the course of the first step of process (a),variant (α), according to the invention can be illustrated by thefollowing equation: ##STR81## If2-(1-chloro-cyclopropyl)-1-(2-chloro-phenyl)-3-(1,2,4-triazol-1-yl)-propan-2-olis used as starting substance, sulphur powder as reactant andN-methyl-pyrrolidone as diluent, the course of the first step of process(a), variant (β), according to the invention can be illustrated by thefollowing equation: ##STR82## If 2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(5-mercapto-1,2,4-triazol -1-yl)-propan-2-ol isused as starting substance and methyl iodide as a reactant, the courseof the second step of process (a) according to the invention can beillustrated by the following equation: ##STR83## If2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(5-methylthio-1,2,4-triazol-1-propan-2-olis used as starting substance and an excess of hydrogen peroxide asoxidant, the course of the third step of process (a) according to theinvention can be illustrated by the following equation: ##STR84## If2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-olis used as starting substance, n-butyl-lithium as strong base anddiphenyl disulphide as reactant, the course of the first step of process(b) according to the invention can be illustrated by the followingequation: ##STR85## If2-(-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(5-phenylthio-1,2,4-triazol-1-yl)-propan-2-olis used and reacted with an equimolar amount of hydrogen peroxide asoxidant, the course of the second step of process (b) according to theinvention can be illustrated by the following equation: ##STR86## If2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(5-mercapto-1,2,4-triazol-1-yl)-propan-2-olis used as starting substance and potassium permanganate as oxidant, thecourse of process (c) according to the invention can be illustrated bythe following equation: ##STR87## Formula (II) provides a generaldefinition of the hydroxyethyl-triazoles required as starting substancesfor carrying out process (a) according to the invention. In thisformula, R¹ and R² preferably have those meanings which have alreadybeen mentioned in connection with the description of the substances ofthe formula (I) according to the invention as being preferred for theseradicals.

The hydroxyethyl-triazoles of the formula (II) are known or can beprepared by known methods (cf. EP-A 0 015 756, EP-A 0 040 345, EP-A 0052 424, EP-A 0 061 835, EP-A 0 297 345 and EP-A 0 470 463).

Suitable bases for carrying out the first step of process (a), variant(α), according to the invention are all strong alkali metal bases whichare customary for such reactions. The following can preferably be used:n-butyl-lithium, lithium diisopropylamide, sodium hydride, sodium amideand also potassium tert-butylate as a mixture withtetramethylethylene-diamine (=TMEDA).

When carrying out the first step of process (a), variant (α), accordingto the invention, suitable diluents are all inert organic solvents whichare customary for such reactions. The following can preferably be used:ethers, such as tetrahydrofuran, dioxane, diethyl ether and1,2-dimethoxyethane, furthermore liquid ammonia or else strongly polarsolvents, such as dimethyl sulphoxide.

Sulphur is preferably employed in the form of a powder. For thehydrolysis when carrying out the first step of process (a), variant (α),according to the invention, water is used, if appropriate in thepresence of an acid. Suitable acids are all inorganic or organic acidswhich are customary for such reactions. Acetic acid, dilute sulphuricacid and dilute hydrochloric acid can preferably be used. However, thehydrolysis can also be carried out using aqueous ammonium chloridesolution.

When carrying out the first step of process (a), variant (α), accordingto the invention, the reaction temperatures can be varied within acertain range. In general, the process is carried out at temperaturesbetween -70° C. and +20° C., preferably between -70° C. and 0° C.

All steps of process (a) according to the invention are generallycarried out under atmospheric pressure. However, it is also possible towork at elevated or reduced pressure. Especially when carrying out thefirst step of process (a) according to the invention according tovariant (α), working at increased pressure is suitable.

When carrying out the first step of process (a) according to theinvention according to variant (α), 2 to 3 equivalents, preferably 2.0to 2.5 equivalents, of strong base and subsequently an equivalent amountor else an excess of sulphur are generally employed relative to 1 mol ofhydroxyethyl-triazole of the formula (II). The reaction can be carriedout under protective gas atmosphere, for example under nitrogen orargon. Working-up is carried out by customary methods. In general, aprocedure is followed in which the reaction mixture is extracted usingan organic solvent which is sparingly soluble in water, the combinedorganic phases are dried and concentrated, and, if desired, the residuewhich remains is purified by recrystallization and/or chromatography.

When carrying out the first step of process (a) according to theinvention according to variant (β), suitable diluents are allhigh-boiling organic solvents which are customary for reactions of thistype. Amides, such as dimethylformamide and dimethylacetamide, can bepreferably used, and additionally heterocyclic compounds, such asN-methyl-pyrrolidone, and also ethers, such as diphenyl ether.

Sulphur is also in general employed in the form of powder when carryingout the first step of process (a) according to the invention accordingto variant (β). After the reaction, if appropriate, a treatment withwater and, if appropriate, with acid can be carried out. This is carriedout like the hydrolysis when carrying out the first step of process (a)according to the invention according to variant (α).

The reaction temperatures can also be varied within a relatively widerange when carrying out the first step of process (a) according to theinvention according to variant (β). In general, the reaction is carriedout at temperatures between 150° C. and 300° C., preferably between 180°C. and 250° C.

When carrying out the first step of process (a) according to theinvention according to variant (β), in general 1 to 5 mol, preferably1.5 to 3 mol, of sulphur are employed relative to 1 mol ofhydroxyethyl-triazole of the formula (II). Working-up is carried out bycustomary methods. In general, a procedure is followed in which thereaction mixture is extracted using an organic solvent which is onlysparingly soluble in water, the combined organic phases are dried andconcentrated and the residue which remains is optionally freed fromimpurities which are possibly present according to customary methods,such as recrystallization or chromatography.

The compounds of the formula (Ia) which are required as startingsubstances for carrying out the second step of process (a) according tothe invention are substances according to the invention.

Formula (III) provides a general definition of the halogen compoundsrequired as reactants for carrying out the second step of process (a)according to the invention.

R⁴ preferably represents straight-chain or branched alkyl having 1 to 6carbon atoms, it being possible for each of these radicals to bemonosubstituted to trisubstituted by fluorine and/or chlorine, or

represents straight-chain or branched alkenyl having 2 to 6 carbonatoms, it being possible for each of these radicals to bemonosubstituted to trisubstituted by fluorine and/or chlorine, or

represents phenylalkyl having 1 to 4 carbon atoms in the straight-chainor branched alkyl moiety, it being possible for each of these radicalsto be monosubstituted to trisubstituted in the phenyl moiety byidentical or different substituents from the series consisting ofhalogen, alkyl having 1 to 4 carbon atoms and/or halogenoalkyl having 1to 4 carbon atoms and 1 to 5 halogen atoms.

R⁴ particularly preferably represents straight-chain or branched alkylhaving 1 to 4 carbon atoms, it being possible for each of these radicalsto be monosubstituted to trisubstituted by fluorine and/or chlorine, or

represents straight-chain or branched alkenyl having 2 to 5 carbonatoms, it being possible for each of these radicals to bemonosubstituted to trisubstituted by identical or different substituentsfrom the series consisting of fluorine and/or chlorine, or

represents phenylalkyl having 1 to 3 carbon atoms in the straight-chainor branched alkyl moiety, it being possible for each of these radicalsto be monosubstituted to trisubstituted in the phenyl moiety byidentical or different substituents from the series consisting offluorine, chlorine, bromine, methyl, ethyl, tert-butyl, trichloromethyland/or trifluoromethyl.

R⁴ very particularly preferably represents methyl, ethyl or propyl, itbeing possible for each of these radicals to be monosubstituted totrisubstituted by identical or different substituents from the seriesconsisting of fluorine and chlorine, or

represents allyl, but-2-en-yl or but-3-enyl, it being possible for eachof these radicals to be monosubstituted to trisubstituted by identicalor different substituents from the series consisting of fluorine and/orchlorine, or

represents phenylalkyl having 1 to 2 carbon atoms in the straight-chainor branched alkyl moiety, it being possible for each of these radicalsto be monosubstituted or disubstituted in the phenyl moiety by fluorine,chlorine, bromine, methyl, ethyl, tert-butyl, trichloromethyl and/ortrifluoromethyl.

Hal also preferably represents chlorine, bromine or iodine.

The halogen compounds of the formula (III) are known.

Suitable acid-binding agents for carrying out the second step of process(a) according to the invention are all customary inorganic or organicbases. The following can preferably be used: alkaline earth metalhydroxides or alkali metal hydroxides, such as sodium hydroxide, calciumhydroxide, potassium hydroxide, or else ammonium hydroxide, alkali metalcarbonates, such as sodium carbonate, potassium carbonate, potassiumhydrogen carbonate, sodium hydrogen carbonate, alkali metal acetates oralkaline earth metal acetates, such as sodium acetate, potassiumacetate, calcium acetate, and also tertiary amines, such astrimethylamine, triethylamine, tributylamine, N,N-dimethylaniline,pyridine, N-methyl-piperidine, N,N-dimethylaminopyridine,diazabicyclooctane (DABCO), diazabicyclonone (DBN) ordiazabicycloundecene (DBU).

Suitable diluents for carrying out the second step of the process (a)according to the invention are all inert organic solvents which arecustomary for such reactions. The following can preferably be used:ethers, such as diethyl ether, methyl tert-butyl ether, ethylene glycoldimethyl ether, tetrahydrofuran and dioxane, furthermore nitriles, suchas acetonitrile, and additionally strong polar solvents, such asdimethyl sulphoxide or dimethylformamide.

When carrying out the second step of process (a) according to theinvention, the reaction temperatures can be varied within a relativelywide range. In general, the process is carried out at temperaturesbetween 0° C. and 120° C., preferably between 20° C. and 100° C.

When carrying out the second step of process (a) according to theinvention, 1 to 2 mol of halogen compound of the formula (III) and anequivalent amount or else an excess of acid-binding agent are generallyemployed relative to 1 mol of triazolyl derivative of the formula (Ia).Working-up is carried out by customary methods. In general, a procedureis followed in which the reaction mixture is treated with aqueous baseand an organic solvent which is sparingly miscible with water, and theorganic phase is separated off, dried and concentrated. If appropriate,the product obtained can be freed from any impurities still present bycustomary methods, for example by recrystallization.

The compounds of the formula (Ib) which are required as startingsubstances for carrying out the third step of process (a) according tothe invention are substances according to the invention.

Suitable oxidants for carrying out the third step of process (a)according to the invention are all substances conventionally used forthe oxidation of sulphur. The following can preferably be used: hydrogenperoxide and peracids, such as peracetic acid and meta-chloro-perbenzoicacid, and additional inorganic salts such as potassium permanganate.

Suitable diluents for carrying out the third step of process (a)according to the invention are all solvents which are customary for suchreactions. If hydrogen peroxide or peracids are used as oxidants, thenacetic acid or glacial acetic acid is preferably employed as thediluent. If the process is carried out with potassium permanganate beingused as the oxidant, then suitable solvents are preferably water oralcohols, such as tert-butanol.

When carrying out the third step of process (a) according to theinvention, the reaction temperatures can be varied within a certainrange. In general, the process is carried out at temperatures between 0°C. and 100° C., preferably between 10° C. and 100° C.

When carrying out the third step of process (a) according to theinvention, an equivalent amount or an excess of oxidant is generallyemployed relative to 1 mol of compound of the formula (lb). If it isdesired to prepare SO compounds, then the process is generally carriedout using equimolar amounts. If it is intended to synthesize SO₂compounds, an excess of oxidants will be selected. Working-up is carriedout by customary methods. In general, a procedure is followed in whichthe mixture is diluted with ice or water, if appropriate renderedalkaline by adding a base, extracted using an organic solvent which issparingly miscible with water, the combined organic phases are dried andconcentrated and, if desired, the product which forms is recrystallized.If the process is carried out with potassium permanganate in aqueoussolution, a procedure is generally followed in which the solid isfiltered off, washed and dried.

Formula (IV) provides a general definition of the diaryl disulphideswhich are required as reactants for carrying out the first step ofprocess (b) according to the invention.

R⁵ preferably represents phenyl which can be monosubstituted totrisubstituted by identical or different substituents from the seriesconsisting of halogen, alkyl having 1 to 4 carbon atoms andhalogenoalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms.

R⁵ particularly preferably represents phenyl which can bemonosubstituted to trisubstituted by identical or different substituentsfrom the series consisting of fluorine, chlorine, bromine, methyl,ethyl, tert-butyl, trichloromethyl and/or trifluoromethyl.

R⁵ very particularly preferably represents phenyl which can bemonosubstituted or disubstituted by fluorine, chlorine, bromine, methyl,ethyl, tert-butyl, trichloromethyl and/or trifluoromethyl.

The diaryl disulphides of the formula (IV) are known or can be preparedby known methods.

Suitable strong bases for carrying out the first step of process (b)according to the invention are all those strong bases which have alreadybeen mentioned in connection with the description of the first step ofprocess (a) according to the invention.

Diluents which are suitable for carrying out the first step of process(b) according to the invention are all those solvents which have alreadybeen mentioned in connection with the description of the first step ofprocess (a) according to the invention.

The remaining reaction conditions and working-up methods for carryingout the first step of process (b) according to the invention, again,correspond to those which have already been mentioned in connection withthe description of the first step of process (a) according to theinvention.

Suitable oxidants for carrying out the second step of process (b)according to the invention are all those oxidants which have alreadybeen mentioned in connection with the description of the third step ofprocess (a) according to the invention.

The reaction conditions and working-up methods for carrying out thesecond step of process (b) according to the invention, again, areanalogous to those which have already been mentioned in connection withthe description of the third step of process (a) according to theinvention. The same applies for the procedure of process (c) accordingto the invention.

The triazolyl derivatives of the formula (I) which can be obtained bythe processes according to the invention can be converted to acidaddition salts or metal salt complexes.

Suitable acids for the preparation of acid addition salts of thecompounds of the formula (I) are preferably those which have alreadybeen mentioned in connection with the description of the acid additionsalts according to the invention as being preferred acids.

Acid addition salts of the compounds of the formula (I) can be obtainedin a simple manner by customary salt formation methods, for example bydissolving a compound of the formula (I) in a suitable inert solvent andadding the acid, for example hydrochloric acid, and they can be isolatedin a known manner, for example by filtering off, and, if appropriate,purified by washing with an inert organic solvent.

Suitable salts for the preparation of metal salt complexes of thecompounds of the formula (I) are preferably those of metals which havealready been mentioned in connection with the description of the metalsalt complexes according to the invention as being preferred metalsalts.

The metal salt complexes of the compounds of the formula (I) can beobtained in a simple manner by customary processes, for example bydissolving the metal salt in alcohol, for example ethanol, and addingthe solution to compounds of the formula (I). Metal salt complexes canbe isolated in a known manner, for example by filtering off, and, ifappropriate, purified by recrystallization.

The active compounds according to the invention have a powerfulmicrobicidal action and can be employed to control undesirablemicroorganisms, such as fungi and bacteria, in plant protection andmaterials protection.

Fungicides are employed in plant protection for combatingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes and Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

Some causative organisms of fungal and bacterial diseases which comeunder the generic names listed above may be mentioned as examples, butnot by way of limitation:

Xanthomonas species, such as Xanthomonas oryzae;

Pseudomonas species, such as Pseudomonas lachrymans;

Erwinia species, such as Erwinia amylovora;

Pythium species, such as Pythium ultimum;

Phytophthora species, such as Phytophthora infestans;

Pseudoperonospora species, such as Pseudoperonospora humuli orPseudoperonospora cubensis;

Plasmopara species, such as Plasmopara viticola;

Peronospora species, such as Peronospora pisi or P. brassicae;

Erysiphe species, such as Erysiphe graminis;

Sphaerotheca species, such as Sphaerotheca fuliginea;

Podosphaera species, such as Podosphaera leucotricha;

Venturia species, such as Venturia inaequalis;

Pyrenophora species, such as Pyrenophora teres or P. graminea (conidiaform: Drechslera, syn: Helminthosporium);

Cochliobolus species, such as Cochliobolus sativus, (conidia form:Drechslera, syn: Helminthosporium);

Uromyces species, such as Uromyces appendiculatus;

Puccinia species, such as Puccinia recondita;

Tilletia species, such as Tilletia caries;

Ustilago species, such as Ustilago nuda or Ustilago avenae;

Pellicularia species, such as Pellicularia sasakii;

Pyricularia species, such as Pyricularia oryzae;

Fusarium species, such as Fusarium culmorum;

Botrytis species, such as Botrytis cinerea;

Septoria species, such as Septoria nodorum;

Leptosphaeria species, such as Leptosphaeria nodorum;

Cercospora species, such as Cercospora canescens;

Alternaria species, such as Alternaria brassicae and

Pseudocercosporella species, such as Pseudocercosporellaherpotrichoides.

The good toleration, by plants, of the active compounds, at theconcentrations required for combating plant diseases, permits treatmentof above-ground parts of plants, of vegetative propagation stock andseeds, and of the soil.

The active compounds according to the invention are particularlysuitable for combating Pyricularia oryzae and Pellicularia sasakii inrice and for combating cereal diseases, such as Pseudocercosporella,Erysiphe species and Fusarium species. Moreover, the substancesaccording to the invention can be employed very successfully againstVenturia and Sphaerotheca. In addition, they also have a very goodin-vitro action.

In materials protection, the substances according to the invention canbe employed for the protection of industrial materials from attack anddestruction by undesirable microorganisms.

Industrial materials in the present connection are understood as meaningnon-living materials which have been prepared for use in industry. Forexample, industrial materials which are to be protected from microbialchange or destruction can be adhesives, glues, paper and cardboard,textiles, leather, wood, paints and plastic articles, cooling lubricantsand other materials which can be attacked or decomposed bymicroorganisms. In the context of the materials to be protected,sections of production plants, for example cooling water circulations,may also be mentioned, which can be adversely affected by proliferationof microorganisms. In the context of the present invention, industrialmaterials which may preferably be mentioned are adhesives, glues, paperand cardboard, leather, wood, paints, cooling lubricants andheat-transfer fluids, particularly preferably wood.

Microorganisms which can cause breakdown or change of the industrialmaterials are, for example, bacteria, fungi, yeasts, algae and slimeorganisms. The active compounds according to the invention preferablyact against fungi, in particular mould fungi, wood-discolouring andwood-destroying fungi (Basidiomycetes) and against slime organisms andalgae.

For example, microorganisms of the following genera may be mentioned:

Alternaria, such as Alternaria tenuis,

Aspergillus, such as Aspergillus niger,

Chaetomium, such as Chaetomium globosum,

Coniophora, such as Coniophora puetana,

Lentinus, such as Lentinus tigrinus,

Penicillium, such as Penicillium glaucum,

Polyporus, such as Polyporus versicolor,

Aureobasidium, such as Aureobasidium pullulans,

Sclerophoma, such as Sclerophoma pityophila,

Trichoderma, such as Trichoderma viride,

Escherichia, such as Escherichia coli,

Pseudomonas, such as Pseudomonas aeruginosa,

Staphylococcus, such as Staphylococcus aureus.

Depending on their particular physical and/or chemical properties, theactive compounds can be converted into the customary formulations, suchas solutions, emulsions, suspensions, powders, foams, pastes, granules,aerosols, very fine capsules in polymeric substances and into coatingcompositions for seeds, as well as ULV cold and warm mist formulations.

These formulations are prepared in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurface-active agents, that is, emulsifying agents and/or dispersingagents, and/or foam-forming agents. In the case of the use of water asan extender, organic solvents can, for example, also be used asauxiliary solvents. As liquid solvents, there are suitable in the main:aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinatedaromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons, such ascyclohexane or paraffins, for example mineral oil fractions, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethyl sulphoxide, as well as water; by liquefied gaseous extenders orcarriers are meant liquids which are gaseous at ambient temperature andunder atmospheric pressure, for example aerosol propellants, such asbutane, propane, nitrogen and carbon dioxide; as solid carriers thereare suitable: for example ground natural minerals, such as kaolins,clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceousearth, and ground synthetic minerals, such as highly disperse silica,alumina and silicates; as solid carriers for granules there aresuitable: for example crushed and fractionated natural rocks such ascalcite, marble, pumice, sepiolite and dolomite, as well as syntheticgranules of inorganic and organic meals, and granules of organicmaterial such as sawdust, coconut shells, maize cobs and tobacco stalks;as emulsifying and/or foam-forming agents there are suitable: forexample non-ionic and anionic emulsifiers, such as polyoxyethylene fattyacid esters, polyoxyethylene fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates aswell as albumen hydrolysis products; as dispersing agents there aresuitable: for example lignin-sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general comprise between 0.1 and 95 per cent byweight of active compound, preferably between 0.5 and 90%.

When used in plant protection, the active compounds according to theinvention can be used as such or, in their formulations, also as amixture with known fungicides, bactericides, acaricides, nematicides orinsecticides, for example so as to widen the spectrum of action or toprevent the build up of resistance. In many cases, this results insynergistic effects, i.e. the activity of the mixture exceeds theactivity of the individual components.

Suitable components for the mixtures are, for example, the followingsubstances:

Fungicides:

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine;2',6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoro-methyl-1,3-thiazole-5-carboxanilide;2,6-dichloro-N-(4-trifluoromethylbenzyl)benzamide;(E)-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)-acetamide;8-hydroxyquinoline sulphate; methyl (E)-2-{2-6-(2-cyanophenoxy)-pyrimidin-4-yloxy!-phenyl}-3-methoxyacrylate; methyl(E)-methoximino alpha-(o-tolyloxy)-o-tolyl!acetate; 2-phenylphenol(OPP), aldimorph, ampropylfos, anilazine, azaconazole,

benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol,blasticidin-S, bromuconazole, bupirimate, buthiobate,

calcium polysulphide, captafol, captan, carbendazim, carboxin,quinomethionate, chloroneb, chloropicrin, chlorothalonil, chlozolinate,cufraneb, cymoxanil, cyproconazole, cyprofuram,

dichlorophen, diclobutrazol, diclofluanid, diclomezin, dicloran,diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole,dinocap, diphenylamine, dipyrithion, ditalimfos, dithianon, dodine,drazoxolon, edifenphos, epoxyconazole, ethirimol, etridiazole,

fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil,fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam,ferimzone, fluazinam, fludioxonil, fluoromide, fluquinconazole,flusilazole, flusulfamide, flutolanil, flutriafol, folpet,fosetyl-aluminium, fthalide, fuberidazole, furalaxyl, furmecyclox,

guazatine,

hexachlorobenzene, hexaconazole, hymexazol,

imazalil, imibenconazole, iminoctadine, iprobenfos (IBP), iprodione,isoprothiolane,

kasugamycin, copper preparations such as: copper hydroxide, coppernaphthenate, copper oxychloride, copper sulphate, copper oxide,oxine-copper and Bordeaux mixture,

mancopper, mancozeb, maneb, mepanipyrim, mepronil, metalaxyl,metconazole, methasulfocarb, methfuroxam, metiram, metsulfovax,myclobutanil,

nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,

ofurace, oxadixyl, oxamocarb, oxycarboxin,

pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin,polyoxin, probenazole, prochloraz, procymidone, propamocarb,propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil,pyroquilon,

quintozene (PCNB),

sulphur and sulphur preparations,

tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole,thicyofen, thiophanate-methyl, thiram, tolclophos-methyl, tolylfluanid,triadimefon, triadimenol, triazoxide, trichlamide, tricyclazole,tridemorph, triflumizole, triforine, triticonazole,

validamycin A, vinclozolin,

zineb, ziram.

Bactericides:

bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,kasugamycin, octhilinone, furanecarboxylic acid, oxytetracyclin,probenazole, streptomycin, tecloftalam, copper sulphate and other copperpreparations.

Insecticides/Acaricides/Nematicides:

abamectin, AC 303 630, acephate, acrinathrin, alanycarb, aldicarb,alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A,azinphos M, azocyclotin,

Bacillus thuringiensis, bendiocarb, benfuracarb, bensultap,beta-cyfluthrin, bifenthrin, BPMC, brofenprox, bromophos A, bufencarb,buprofezin, butocarboxin, butylpyridaben,

cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap,CGA 157 419, CGA 184699, chloethocarb, chlorethoxyfos chlorfenvinphos,chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M,cis-resmethrin, clocythrin, clofentezine, cyanophos, cycloprothrin,cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,

deltamethrin, demeton-M, demeton-S, demeton-S-methyl, diafenthiuron,diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion,diflubenzuron, dimethoate, dimethylvinphos, dioxathion, disulfoton,

edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion, ethofenprox,ethoprophos, etrimphos,

fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb,fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate,fenthion, fenvalerate, fipronil, fluazinam, flucycloxuron,flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonophos,formothion, fosthiazate, fubfenprox, furathiocarb,

HCH, heptenophos, hexaflumuron, hexythiazox,

imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb, isoxathion,ivemectin,

lambda-cyhalothrin, lufenuron,

malathion, mecarbam, mervinphos, mesulfenphos, metaldehyde, methacrifos,methamidophos, methidathion, methiocarb, methomyl, metolcarb,milbemectin, monocrotophos, moxidectin,

naled, NC 184, NI 25, nitenpyram,

omethoate, oxamyl, oxydemethon M, oxydeprofos,

parathion A, parathion M, permethrin, phenthoate, phorate, phosalone,phosmet, phosphamdon, phoxim, pirimicarb, pirimiphos M, pirimiphos A,profenofos, promecarb, propaphos, propoxur, prothiofos, prothoate,pymetrozin, pyrachlophos, pyridaphenthion, pyresmethrin, pyrethrum,pyridaben, pyrimidifen, pyriproxifen,

quinalphos,

RH 5992,

salithion, sebufos, silafluofen, sulfotep, sulprofos,

tebufenozid, tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin,temephos, terbam, terbufos, tetrachlorvinphos, thiafenox, thiodicarb,thiofanox, thiomethon, thionazin, thuringiensin, tralomethrin,triarathen, triazophos, triazuron, trichlorfon, triflumuron,trimethacarb,

vamidothion, XMC, xylylcarb, zetamethrin.

A mixture with other known active compounds, such as herbicides, or withfertilizers and growth regulators, is also possible.

The active compounds can be used as such or in the form of theirformulations or the application forms prepared therefrom, such asready-to-use solutions, emulsifiable concentrates, emulsions, foams,suspensions, wettable powders, pastes, soluble powders, dusts andgranules. They are used in the customary manner, for example bywatering, spraying, atomizing, scattering, dusting, foaming, brushing onand the like. It is furthermore possible to apply the active compoundsby the ultra-low volume method or to inject the active compoundformulation or the active compound itself into the soil. The seeds ofthe plants can also be treated.

In the treatment of parts of plants, the active compound concentrationsin the application forms can be varied within a relatively wide range:in general, they are between 1 and 0.0001% by weight, preferably between0.5 and 0.001% by weight.

In the treatment of seed, in general amounts of active compound from0.001 to 50 g per kilogram of seed are needed, preferably 0.01 to 10 g.

In the treatment of the soil, active compound concentrations of 0.00001to 0.1% by weight are necessary at the site of action, preferably from0.0001 to 0.02% by weight.

The compositions used for the protection of industrial materials ingeneral contain the active compounds in an amount from 1 to 95%,preferably from 10 to 75%.

The application concentrations of the active compounds according to theinvention depend on the nature and the occurrence of the microorganismsto be controlled and on the composition of the material to be protected.The optimum amount to be employed can be determined by a series oftests. In general, the application concentrations are in the range from0.001 to 5% by weight, preferably from 0.05 to 1.0% by weight, based onthe material to be protected.

The activity and the spectrum of action of the active compounds to beused in materials protection or the compositions, concentrates or, verygenerally, formulations which can be prepared therefrom can be increasedif further antimicrobially active compounds, fungicides, bactericides,herbicides, insecticides or other active compounds are optionally addedto increase the spectrum of action or achieve particular effects suchas, for example, additional protection from insects. These mixtures canhave a wider spectrum of action than the compounds according to theinvention.

Preparation and use of the substances according to the invention can beseen from the examples which follow.

PREPARATION EXAMPLES Example 1 ##STR88## Variant α

A mixture of 3.12 g (10 mmol) of2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-oland 45 ml of absolute tetrahydrofuran is treated at 20° C. with 8.4 ml(21 mmol) of n-butyl-lithium in hexane, and the mixture is stirred at 0°C. for 30 minutes. The reaction mixture is then cooled to -70° C., 0.32g (10 mmol) of sulphur powder are added, and the mixture is stirred for30 minutes at -70° C. It is heated to -10° C., and treated withice-water and brought to a pH of 5 by adding dilute sulphuric acid. Themixture is extracted repeatedly using ethyl acetate, and the combinedorganic phases are dried over sodium sulphate and concentrated underreduced pressure. In this manner, 3.2 g (93% of theory) of2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(5-mercapto-1,2,4-triazol-1-yl)-propan-2-olare obtained in the form of a solid which, after recrystallization,melts at 138°-139° C.

Variant β

A mixture of 3.12 g (10 mmol) of2-(1-chloro-cyclopropyl)-1-(2-chloro-phenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol,0.96 g (30 mmol) of sulphur powder and 20 ml of absoluteN-methyl-pyrrolidone is heated at 200° C. for 44 hours with stirring.The reaction mixture is then concentrated under reduced pressure (0.2mbar). The crude product which is obtained (3.1 g) is recrystallizedfrom toluene. In this manner, 0.7 g (20% of theory) of2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(5-mercapto-1,2,4-triazol-1-yl)-propan-2-olis obtained in the form of a solid substance of melting point 138°-139°C.

Example 2 ##STR89##

A mixture of 3.43 g (10 mmol) of2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(5-mercapto-1,2,4-triazol-1-yl)-propan-2-ol,20 ml of absolute acetonitrile and 1.38 g of (10 mmol) of potassiumcarbonate is treated with 0.93 ml (15 mmol) of methyl iodide and themixture is stirred at 40° C. for 5 hours. The reaction mixture is thentreated with saturated, aqueous sodium carbonate solution and extractedrepeatedly using ethyl acetate. The combined organic phases are driedover sodium sulphate and concentrated under reduced pressure. In thismanner, 3.4 g (95% of theory) of2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(5-methylthio-1,2,4-triazol-1-yl)-propan-2-olare obtained in the form of oil.

¹ H NMR spectrum (200 MHz; CDCl₃, TMS): δ=0.6-1.05 (m, 4H); 2.7 (s, 3H);3.35 (AB, 2H); 4.4 (AB, 2H); 4.7 (OH); 7.2-7.6 (m, 4H); 7.9 (s, 1H).

Example 3 ##STR90##

A solution of 3.57 g (10 mmol) of2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-3-(5-methylthio-1,2,4-triazol-1-yl)-propan-2-olin 40 ml of glacial acetic acid is treated dropwise at 90° C. withstirring with 4 ml of an aqueous hydrogen peroxide solution (35%strength). After the addition has ended, stirring of the reactionmixture is continued at 90° C. for 30 minutes, and the mixture is thencooled to room temperature, treated with ice and rendered alkaline byadding aqueous sodium hydroxide solution. The mixture is extractedrepeatedly using ethyl acetate, and the combined organic phases aredried over sodium sulphate and concentrated under reduced pressure. Theslowly crystallizing product which remains is filtered off with suction.In this manner, 2.0 g (51% of theory) of2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(5-methylsulphonyl-1,2,4-triazol-1-yl)-propan-2-ol)are obtained in the form of a solid which melts at 125°-128° C.

Example 4 ##STR91##

A mixture of 1.71 g (5 mmol) of2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-3-(5-mercapto-1,2,4-triazol-1-yl)-propan-2-ol,1.58 g (10 mmol) of potassium permanganate and 20 ml of water is stirredat room temperature for 30 minutes. The solid is then filtered off withsuction, washed with water and dried. In this manner, 2.0 g (100% oftheory) of2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(5-sulpho-1,2,4-triazol-1-yl)-propan-2-olare obtained in the form of a solid which melts at 68°-70° C.

Example 5 ##STR92##

A mixture of 3.12 g (10 mmol) of2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-oland 45 ml of absolute tetrahydrofuran is treated at -20° C. with 8.4 ml(21 mmol) of n-butyl-lithium in hexane and the mixture is stirred at 0°C. for 30 minutes. The reaction mixture is then cooled to -70° C.,treated with 2.18 g (10 mmol) of diphenyl disulphide and slowlydefrosted to room temperature, with stirring. Stirring is continued foranother 19 hours at room temperature, and the mixture is diluted withethyl acetate and repeatedly extracted by shaking with saturated aqueoussodium carbonate solution. The organic phase is dried over sodiumsulphate and concentrated under reduced pressure. The 4.2 g of residuewhich remains is chromatographed over 500 g of silica gel using amixture of petroleum ether/ethyl acetate=2:1. After the eluate hasevaporated, 3.5 g (84% of theory) of2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(5-phenylthio-1,2,4-triazol-1-yl)-propan-2-olare obtained in the form of an oil.

Mass spectrum (Cl): 420 (M+H⁺)

Example 6 ##STR93##

A mixture of 1.41 g (5 mmol) of1,2-dichloro-4,4-dimethyl-5-fluoro-3-hydroxy-3-(1,2,4-triazol-1-yl)-methyl!-1-pentene and 25 ml of absolutetetrahydrofuran is treated at -70° C. with 4 ml (10 mmol) ofn-butyl-lithium in hexane and the mixture is stirred at -70° C. for onehour. The reaction mixture is then treated with 0.19 g (6 mmol) ofsulphur powder and stirred at -70° C. for 4 hours. It is then hydrolysedby adding 1 ml of methanol and 1 ml of acetic acid at -70° C. Thereaction mixture is first diluted with ethyl acetate and then extractedby shaking several times with saturated, aqueous ammonium chloridesolution. The organic phase is dried over sodium sulphate andconcentrated under reduced pressure. The crude product (1.7 g) which isobtained is purified by chromatography on silica gel using a mixture ofpetroleum ether and ethyl acetate=1:1 as eluent. In this way, 0.5 g (32%of theory) of 1,2-dichloro-4,4-dimethyl-5-fluoro-3-hydroxy-3-(5-mercapto-1,2,4-triazol-1-yl)-methyl!-1-pentene is obtained in theform of a solid substance of melting point 162°-164° C.

The substances shown in the following Table 2 are also preparedaccording to the methods indicated previously.

                                      TABLE 2                                     __________________________________________________________________________     ##STR94##                                                                    Ex.                                                                              Compound                          Physical                                 No.                                                                              No.   R.sup.1        R.sup.2      constant                                 __________________________________________________________________________     7 (I-7) CClCHCl        C(CH.sub.3).sub.3                                                                          M.p. 168-                                                                     169° C.                            8 (I-8)                                                                                ##STR95##                                                                                    ##STR96##   GC/MS (Cl): 376 (M + H.sup.+)             9 (I-9)                                                                                ##STR97##                                                                                    ##STR98##   M.p. 163- 164° C.                 10 (I-10)                                                                               ##STR99##     C(CH.sub.3).sub.3                                                                          M.p. 127° C.                      11 (I-11)                                                                               ##STR100##                                                                                   ##STR101##  Oil                                      12 (I-12)                                                                               ##STR102##                                                                                   ##STR103##  GC/MS (Cl): 340 (M + H.sup.+)            13 (I-13)                                                                               ##STR104##                                                                                   ##STR105##  GC/MS (Cl): 424 (M + H.sup.+)            14 (I-14)                                                                               ##STR106##                                                                                   ##STR107##  M.p. 168° C.                      15 (I-15)                                                                               ##STR108##                                                                                   ##STR109##  GC/MS (Cl): 314 (M + H.sup.+)            16 (I-16)                                                                               ##STR110##                                                                                   ##STR111##  GC/MS (Cl): 346 (M + H.sup.+)            17 (I-17)                                                                               ##STR112##                                                                                   ##STR113##  M.p. 115- 118° C.                 18 (I-18)                                                                               ##STR114##    C(CH.sub.3).sub.3                                                                          GC/MS (Cl): 340 (M + H.sup.+)            19 (I-19)                                                                               ##STR115##                                                                                   ##STR116##  GC/MS (Cl): 334 (M + H.sup.+)            20 (I-20)                                                                               ##STR117##    C.sub.4 H.sub.9 -n                                                                         *)                                       __________________________________________________________________________     *) The compound is characterized by the following signals in the .sup.1       HNMR spectrum (400 MHz, CDCl.sub.3 /TMS):                                     δ = 0.8(t, 3H); 0.85(m, 2H); 1.25(m, 2H); 1.8(m, 1H); 2.55(m, 1H);      4.6(OH); 4.9(AB, 2H); 7.2(dd, 1H); 7.35(d, 1H); 7.7(s, 1H); 7.75(d, 1H);      12.3(5H)ppm                                                              

USE EXAMPLES Example A

Erysiphe test (barley)/protective

Solvent: 10 parts by weight of N-methyl-pyrrolidone

Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the application rate shown. After thespray coating has dried on, the plants are dusted with spores ofErysiphe graminis f.sp.hordei.

The plants are placed in a greenhouse at a temperature of about 20° C.and a relative atmospheric humidity of about 80%, in order to promotethe development of mildew pustules.

Evaluation is carried out 7 days after the inoculation.

The active compounds, active compound concentrations and test resultsare shown in the following table.

                  TABLE A                                                         ______________________________________                                        Erysiphe test (barley)/protective                                                              Degree of effectiveness in % of the                                           untreated control at an active com-                          Active compound  pound application rate of 250 g/ha                           ______________________________________                                        According to the invention:                                                    ##STR118##      100                                                          ______________________________________                                    

Example B

Erysiphe test (wheat)/protective

Solvent: 10 parts by weight of N-methyl-pyrrolidone

Emulsifier: 10 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the application rate shown. After thespray coating has dried on, the plants are dusted with spores ofErysiphe graminis f.sp. tritici.

The plants are placed in a greenhouse at a temperature of about 20° C.and a relative atmospheric humidity of about 80%, in order to promotethe development of mildew pustules.

Evaluation is carried out 7 days after the inoculation.

The active compounds, active compound concentrations and test resultsare shown in the following table.

                  TABLE B                                                         ______________________________________                                        Erysiphe test (wheat)/protective                                                               Degree of effectiveness in % of the                                           untreated control at an active com-                          Active compound  pound application rate of 250 g/ha                           ______________________________________                                        According to the invention:                                                    ##STR119##      100                                                          ______________________________________                                    

Example C

Pseudocercosporella herpotrichoides test (wheat)/protective

Solvent: 10 parts by weight of N-methyl-pyrrolidone

Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the application rate shown. After thespray coating has dried on, the stem base of the plants is inoculatedwith spores of Pseudocercosporella herpotrichoides.

The plants are placed in a greenhouse at a temperature of about 10° C.and a relative atmospheric humidity of about 80%.

Evaluation is carried out 21 days after the inoculation.

The active compounds, active compound concentrations and test resultsare shown in the following table.

                  TABLE C                                                         ______________________________________                                        Pseudocercosporella herpotrichoides test (wheat)/protective                                    Degree of effectiveness in % of the                                           untreated control at an active                               Active compound  compound application rate of 25 g/ha                         ______________________________________                                        According to the invention:                                                    ##STR120##      100                                                          Disclosed in EP-A 0 297 345:                                                   ##STR121##       75                                                          ______________________________________                                    

Example D

Fusarium nivale (var. nivale) test (wheat)/protective

Solvent: 10 parts by weight of N-methyl-pyrrolidone

Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the application rate shown. After thespray coating has dried on, the plants are sprayed with a conidiasuspension of Fusarium nivale var. nivale.

The plants are placed in a greenhouse under transparent incubation cagesat a temperature of about 15° C. and a relative atmospheric humidity ofabout 100%.

The active compounds, active compound concentrations and test resultsare shown in the following table.

                  TABLE D                                                         ______________________________________                                        Fusarium nivale (var. nivale) test (wheat)/protective                                          Degree of effectiveness in % of the                                           untreated control at an active com-                          Active compound  pound application rate of 250 g/ha                           ______________________________________                                        According to the invention:                                                    ##STR122##      100                                                          ______________________________________                                    

Example E

Fusarium culmorum test (wheat)/protective

Solvent: 10 parts by weight of N-methyl-pyrrolidone

Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the application rate shown. After thespray coating has dried on, the plants are sprayed with a conidiasuspension of Fusarium culmorum.

The plants are placed in a greenhouse under transparent incubation cagesat a temperature of about 20° C. and a relative atmospheric humidity ofabout 100%.

Evaluation is carried out 4 days after the inoculation.

The active compounds, active compound concentrations and test resultsare shown in the following tables.

                  TABLE E-1                                                       ______________________________________                                        Fusarium culmorum test (wheat)/protective                                                      Degree of effectiveness in % of the                                           untreated control at an active com-                          Active compound  pound application rate of 250 g/ha                           ______________________________________                                        According to the invention:                                                    ##STR123##      100                                                          ______________________________________                                    

                  TABLE E-2                                                       ______________________________________                                        Fusarium culmorum test (wheat)/protective                                                        Degree of effectiveness in % of                                               the untreated control at an active                                            compound application rate of                               Active compound    25 g/ha                                                    ______________________________________                                        Disclosed in EP-A 0 461 502:                                                   ##STR124##        50                                                         According to the invention:                                                    ##STR125##        75                                                         ______________________________________                                    

                  TABLE E-3                                                       ______________________________________                                        Fusarium culmorum test (wheat)/protective                                                      Degree of effectiveness in % of the                                           untreated control at an active com-                          Active compound  pound application rate of 125 g/ha                           ______________________________________                                        Disclosed in EP-A 0 564 810:                                                   ##STR126##       88                                                          According to the invention:                                                    ##STR127##      100                                                          ______________________________________                                    

Example F

Pellicularia-Test (rice)

Solvent: 12.5 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, and theconcentrate is diluted with water and the stated amount of emulsifier tothe desired concentration.

To test for activity, young rice plants in the 3 to 4 leaf stage aresprayed until dripping wet. The plants remain in a greenhouse until theyhave dried. The plants are then inoculated with Pellicularia sasakii andare placed at 25° C. and 100% relative atmospheric humidity.

The evaluation of the disease infestation is carried out 5 to 8 daysafter the inoculation.

The active compounds, active compound concentrations and test resultsare shown in the following table.

                  TABLE F                                                         ______________________________________                                        Pellicularia test (rice)                                                                       Active compound                                                                           Degree of                                                         concentration in                                                                          effectiveness in %                                                the spray mixture                                                                         of the untreated                                 Active compound  in % by weight                                                                            control                                          ______________________________________                                        According to the invention:                                                    ##STR128##      0.025       100                                              ______________________________________                                    

Example G

Sphaerotheca test (cucumber)/protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, the plants are dusted with conidia of the fungusSphaerotheca fuliginea.

The plants are then placed in a greenhouse at 23° to 24° C. and at arelative atmospheric humidity of about 75%.

Evaluation is carried out 10 days after the inoculation.

The active compounds, active compound concentrations and test resultsare shown in the following table.

                  TABLE G                                                         ______________________________________                                        Sphaerotheca test (cucumber)/protective                                                        Degree of effectiveness in % of the                                           untreated control at an active                               Active compound  compound application rate of 1 ppm                           ______________________________________                                        According to the invention:                                                    ##STR129##      100                                                          ______________________________________                                    

We claim:
 1. A triazolyl derivative of the formula ##STR130## in whichR¹ represents straight-chain or branched alkyl having 1 to 6 carbonatoms, wherein these radicals are optionally monosubstituted totetrasubstituted by identical or different substituents selected fromthe group consisting of halogen, alkoxy having 1 to 4 carbon atoms,alkoximino having 1 to 4 carbon atoms in the alkoxy moiety, andcycloalkyl having 3 to 7 carbon atoms, orR¹ represents cycloalkyl having3 to 7 carbon atoms, wherein these radicals are optionallymonosubstituted to trisubstituted by identical or different substituentsselected from the group consisting of halogen, cyano and alkyl having 1to 4 carbon atoms, or R¹ represents aralkyl having 6 to 10 carbon atomsin the aryl moiety and 1 to 4 carbon atoms in the straight-chain orbranched alkyl moiety, wherein the aryl moiety is optionallymonosubstituted to trisubstituted by identical or different substituentsselected from the group consisting of halogen, alkyl having 1 to 4carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4carbon atoms, halogenoalkyl having 1 to 2 carbon atoms and 1 to 5identical or different halogen atoms, halogenoalkylthio having 1 to 2carbon atoms and 1 to 5 identical or different halogen atoms, cycloalkylhaving 3 to 7 carbon atoms, phenyl, phenoxy, alkoxycarbonyl having 1 to4 carbon atoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkylmoiety, nitro and cyano, or R¹ represents aroxyalkyl having 6 to 10carbon atoms in the aryl moiety and 1 to 4 carbon atoms in thestraight-chain or branched oxyalkyl moiety, wherein the aryl moiety isoptionally substituted monosubstituted to trisubstituted by identical ordifferent substituents selected from the group consisting of halogen,alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms,alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 to 2 carbonatoms and 1 to 5 identical or different halogen atoms, halogenoalkoxyhaving 1 to 2 carbon atoms and 1 to 5 identical or different halogenatoms, halogenoalkylthio having 1 to 2 carbon atoms and 1 to 5 identicalor different halogen atoms, cycloalkyl having 3 to 7 carbon atoms,phenyl, phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxymoiety, alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moietyand 1 to 4 carbon atoms in the alkyl moiety, nitro and cyano, or R¹represents aryl having 6 to 10 carbon atoms, wherein each of theseradicals is optionally monosubstituted to trisubstituted by identical ordifferent substituents selected from the group consisting of halogen,alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms,alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 to 2 carbonatoms and 1 to 5 identical or different halogen atoms, halogenoalkoxyhaving 1 to 2 carbon atoms and 1 to 5 identical or different halogenatoms, halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 identicalor different halogen atoms, cycloalkyl having 3 to 7 carbon atoms,phenyl, phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxymoiety, alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moietyand 1 to 4 carbon atoms in the alkyl moiety, nitro and cyano, R²represents straight-chain or branched alkyl having 1 to 6 carbon atoms,wherein these radicals are optionally monosubstituted totetrasubstituted by identical or different substituents selected fromthe group consisting of halogen, alkoxy having 1 to 4 carbon atoms,alkoximino having 1 to 4 carbon atoms in the alkoxy moiety andcycloalkyl having 3 to 7 carbon atoms, or R² represents cycloalkylhaving 3 to 7 carbon atoms, wherein each of these radicals is optionallymonosubstituted to trisubstituted by identical or different substituentsselected from the group consisting of halogen, cyano and alkyl having 1to 4 carbon atoms, or R² represents aralkyl having 6 to 10 carbon atomsin the aryl moiety and 1 to 4 carbon atoms in the straight-chain orbranched alkyl moiety, wherein the aryl moiety in each case isoptionally monosubstituted to trisubstituted by identical or differentsubstituents selected from the group consisting of halogen, alkyl having1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having1 to 4 carbon atoms, halogenoalkyl having 1 to 2 carbon atoms and 1 to 5identical or different halogen atoms, halogenoalkoxy having 1 to 2carbon atoms and 1 to 5 identical or different halogen atoms,halogenoalkylthio having 1 to 2 carbon atoms and 1 to 5 identical ordifferent halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl,phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety,alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to4 carbon atoms in the alkyl moiety, nitro and cyano, or R² representsaroxyalkyl having 6 to 10 carbon atoms in the aryl moiety and 1 to 4carbon atoms in the straight-chain or branched oxyalkyl moiety, whereinthe aryl moiety is optionally substituted monosubstituted totrisubstituted by identical or different substituents selected from thegroup consisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxyhaving 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms,halogenoalkyl having 1 to 2 carbon atoms and 1 to 5 identical ordifferent halogen atoms, halogenoalkoxy having 1 to 2 carbon atoms and 1to 5 identical or different halogen atoms, halogenoalkylthio having 1 to2 carbon atoms and 1 to 5 identical or different halogen atoms,cycloalkyl having 3 to 7 carbon atoms, phenyl, phenoxy, alkoxycarbonylhaving 1 to 4 carbon atoms in the alkoxy moiety, alkoximinoalkyl having1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in thealkyl moiety, nitro and cyano, or R² represents aryl having 6 to 10carbon atoms, wherein each of these radicals is optionallymonosubstituted to trisubstituted by identical or different substituentsselected from the group consisting of halogen, alkyl having 1 to 4carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4carbon atoms, halogenoalkyl having 1 to 2 carbon atoms and 1 to 5identical or different halogen atoms, halogenoalkoxy having 1 to 2carbon atoms and 1 to 5 identical or different halogen atoms,halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 identical ordifferent halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl,phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety,alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to4 carbon atoms in the alkyl moiety, nitro and cyano, x represents thegroups --SH, --SR³, --SO--R³ or --SO₃ H, in which R³ representsstraight-chain or branched alkyl having 1 to 6 carbon atoms, whereineach of these radicals is optionally monosubstituted to trisubstitutedby fluorine and/or chlorine, or R³ represents straight-chain or branchedalkenyl having 2 to 6 carbon atoms, wherein each of these radicals isoptionally monosubstituted to trisubstituted by fluorine and/orchlorine, or R³ represents phenylalkyl having 1 to 4 carbon atoms in thestraight-chain or branched alkyl moiety, wherein each of these radicalsis optionally monosubstituted to trisubstituted in the phenyl moiety byidentical or different substituents selected from the group consistingof halogen, alkyl having 1 to 4 carbon atoms, and halogenoalkyl having 1to 4 carbon atoms and 1 to 5 halogen atoms, or R³ represents phenylwhich is optionally monosubstituted to trisubstituted by identical ordifferent substituents selected from the group consisting of halogen,alkyl having 1 to 4 carbon atoms, and halogenoalkyl having 1 to 4 carbonatoms and 1 to 5 atoms, or an addition product thereof with an acid ormetal salt.
 2. The compound according to claim 1, which has the formula##STR131##
 3. A microbiocidal composition comprising a microbiocidallyeffective amount of a compound or addition product as claimed in claim 1and an inert diluent.
 4. A method of controlling undesiredmicroorganisms in plant protection and in the preservation of materials,which method comprises applying to such undesired microorganisms or totheir habitat a microbiocidally effective amount of a compound oraddition product as claimed in claim 1.